CN101786600B - SnO2/ZnO composite polycrystal nanobelt preparation method - Google Patents
SnO2/ZnO composite polycrystal nanobelt preparation method Download PDFInfo
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- CN101786600B CN101786600B CN201010117282A CN201010117282A CN101786600B CN 101786600 B CN101786600 B CN 101786600B CN 201010117282 A CN201010117282 A CN 201010117282A CN 201010117282 A CN201010117282 A CN 201010117282A CN 101786600 B CN101786600 B CN 101786600B
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Abstract
The invention relates to a SnO2/ZnO composite polycrystal nanobelt preparation method and belongs to the technical field of nano-material preparation. The invention consists of three steps: (1) preparation of spinning solution; SnCl4 and Zn (CH3COO) 2 are dissolved in DMF, and then PVP is added to form the spinning solution; (2) preparation of PVP / (SnCl4 + Zn (CH3COO) 2) composite nanobelt: the electrostatic spinning parameters are as follows: the voltage is 15-20kV; the curing distance is 13-15cm; the room temperature is 20 - 25 DEG C, and the relative humidity is 45%-60%; (3) the preparation of SnO2/ZnO composite polycrystal nanobelt: thermal treatment is carried out on the composite nanobelt to obtain SnO2/ZnO composite polycrystal nanobelt with width of 2-6mum, the thickness of 240-600nm and the length more than 100mum.
Description
Technical field
The present invention relates to the nano material preparation technical field, relate in particular to the preparation method of the compound polycrystal nanobelt of tin ash/zinc oxide.
Background technology
The preparation of inorganic matter nano belt and property research are one of forward position focus of subject researchs such as material science, chemistry, Condensed Matter Physics at present.Nano belt is a kind of nano material that is banded structure of synthesizing with manual method, and its cross section is a rectangular configuration, and its thickness is in nanometer scale, and length can reach the hundreds of micron, even the millimeter level.Nano belt is owing to the performances such as novel structure and unique light, electricity, magnetic that it is different from pipe, wire material receive extensive concern.Though nano belt lacks the high structural capacity that the cylindricality nanotube is had, its production process simple controllable, and can guarantee the material structure homogeneous when producing in a large number, defective is few, thereby causes people's great attention.
SnO
2/ ZnO composite nano materials can be used as the electrode material of antistatic additive, gas sensing modulator material, dye-sensitized solar cells and the photochemical catalyst of degradable organic pollutant etc.The SnO that has prepared at present
2The form of/ZnO composite nano materials comprises: composite nanoparticle and nanofiber etc.Zhou Bingming etc. adopt coprecipitation to prepare SnO
2/ ZnO composite nanoparticle (chemical research and application, 2008,20 (6), 705-709); Dong Ling etc. adopt chemical method to prepare SnO
2/ ZnO composite nanoparticle (petroleum refining and chemical industry, 2005,36 (12), 45-49); Wang Cun, et al adopt coprecipitation to prepare ZnO/SnO
2Nano-photocatalyst (Applied Catalysis B:Environmental, 2002,39 (3), 269-279); Maolin Zhang, et al adopt the homogeneous coprecipitation method to prepare nano-ZnO-SnO
2(Materials Letters, 2005,59 (28), 3641-3644); Chen Liangyuan, et al have adopted prepared by reverse microemulsion method nano-ZnO-SnO
2Composite (Sensors and Actuators B:Chemical, 2008,134 (2), 360-366); Xiaofeng Song, et al adopt electrostatic spinning technique to prepare ZnO-SnO
2Nanofiber (Sensors and Actuators A:Physical, 2009,154 (1), 175-179).
The patent No. is the technical scheme that 1975504 United States Patent (USP) discloses a relevant electrospinning process (electrospinning); This method is a kind of effective ways that prepare continuous, as to have macro length micro nanometer fiber, is at first proposed in 1934 by Formhals.This method mainly is used for preparing high polymer nanometer fiber; It is characterized in that making charged Polymer Solution or melt in electrostatic field, to receive the traction of electrostatic force and spray, invest the receiving screen on opposite, thereby realize wire drawing by nozzle; Then; Solvent evaporation at normal temperatures, perhaps melt is cooled to normal temperature and solidifies, and obtains micro nanometer fiber.Over nearly 10 years, occurred adopting electrospinning process to prepare the technical scheme of inorganic compound such as oxidate nano fiber at the inorfil preparing technical field, described oxide comprises TiO
2, ZrO
2, Y
2O
3, Y
2O
3: RE
3+(RE=Eu, Tb, Er, Er/Yb), NiO, Co
3O
4, Mn
2O
3, Mn
3O
4, CuO, SiO
2, Al
2O
3, V
2O
5, ZnO, Nb
2O
5, MoO
3, CeO
2Deng metal oxide.Existing people utilizes electrostatic spinning technique successfully to prepare high molecular nanometer band (Materials Letters, 2007,61:2325-2328; Journal of PolymerScience:Part B:Polymer Physics, 2001,39:2598-2606).Someone utilizes the organic compound of tin, uses electrostatic spinning technique to combine with the metallo-organic compound decomposition technique and has prepared porous SnO
2Nano belt (Nanotechnology, 2007,18:435704); Someone utilizes electrostatic spinning technique at first to prepare PEO/ stannic hydroxide composite Nano band, and its roasting has been obtained porous SnO
2Nano belt (J.Am.Ceram.Soc., 2008,91 (1): 257-262).Dong Xiangting etc., the employing polymethyl methacrylate is a template, utilizes electrostatic spinning technique to prepare TiO
2Nano belt (Chinese invention patent, application number: 200810050948.2).Do not see SnO at present
2The report of/ZnO composite Nano band.Therefore, SnO
2/ ZnO composite Nano band is a kind of very promising functional material, is again the inorganic matter composite Nano band of novel structure, has broad application prospects.
When utilizing electrostatic spinning technique to prepare nano material, the composition of the kind of raw material, the molecular weight of high polymer templates, spinning solution, spinning process parameter and Technology for Heating Processing all have material impact to the pattern and the size of final products.The present invention adopts electrostatic spinning technique, with butter of tin (SnCl
45H
2O) and zinc acetate (Zn (CH
3COO)
22H
2O) be raw material, polyvinylpyrrolidone (PVP, molecular weight are 90000) is as high polymer templates, N, and dinethylformamide (DMF) is a solvent, under the experiment condition of the best, prepares PVP/ [SnCl
4+ Zn (CH
3COO)
2] the composite Nano band, obtain SnO through after the high-temperature process again
2The compound polycrystal nanobelt of/ZnO.
Summary of the invention
Preparation SnO in background technology
2/ ZnO composite nanoparticle and nanofiber have adopted coprecipitation, homogeneous coprecipitation method, reverse microemulsion process, method of electrostatic spinning etc.; Use electrostatic spinning technique in the background technology prepares high molecular nanometer band, SnO
2Nano belt and TiO
2Nano belt etc., employed raw material, template and solvent are all different with method of the present invention.The present invention uses electrostatic spinning technique to prepare SnO
2The compound polycrystal nanobelt of/ZnO, bandwidth 2～6 μ m, thickness 240～600nm, length is greater than 100 μ m.
The present invention is achieved in that and at first prepares the spinning solution with certain viscosity that is used for electrostatic spinning, uses electrostatic spinning technique and carries out electrostatic spinning, under the experiment condition of the best, prepares PVP/ [SnCl
4+ Zn (CH
3COO)
2] the composite Nano band, obtain SnO through after the high-temperature process again
2The compound polycrystal nanobelt of/ZnO.
The steps include:
(1) preparing spinning solution
What used in Xi Yuan and zinc source in the spinning solution is butter of tin and zinc acetate, and high polymer templates adopts polyvinylpyrrolidone (PVP, molecular weight are 90000).Solvent adopts DMF.Take by weighing a certain amount of butter of tin and zinc acetate (mol ratio is 1: 2), be dissolved in an amount of DMF solvent, take by weighing a certain amount of PVP again and join in the above-mentioned solution, stir 3～6h in the room temperature lower magnetic force, and leave standstill 2～3h, promptly form spinning solution.The mass percent of this each part of spinning solution is: butter of tin+zinc acetate content 8～10%, PVP content 19～22%, DMF content 68～73%.
(2) preparation PVP/ [SnCl
4+ Zn (CH
3COO)
2] the composite Nano band
Adopt electrostatic spinning technique, technical parameter is: DC voltage is 15～20kV; The syringe needle nozzle diameter is 0.8mm; The angle of nozzle and horizontal plane is 15 °; Nozzle is 13～15cm to the curing distance of receiving screen; 20～25 ℃ of indoor temperatures, relative humidity are 45%～60%.
(3) preparation SnO
2The compound polycrystal nanobelt of/ZnO
With the PVP/ [SnCl that is obtained
4+ Zn (CH
3COO)
2] the composite Nano band carries out heat treatment, technical parameter is: heating rate is 1～2 ℃/main, in 600～800 ℃ of temperature ranges, is incubated 8～10h, rate of temperature fall is controlled to be 1 ℃/min, reduces to room temperature when cooling to 200 ℃ naturally, so far obtains SnO
2The compound polycrystal nanobelt of/ZnO.
Prepared PVP/ [SnCl in said process
4+ Zn (CH
3COO)
2] smooth, the prepared SnO of composite Nano belt surface smoother
2/ ZnO is compound, and polycrystal nanobelt is made up of nano particle, and the width of nano belt is 2～6 μ m, and thickness is 240～600nm, and length has realized goal of the invention greater than 100 μ m.
Description of drawings
Fig. 1 is PVP/ [SnCl
4+ Zn (CH
3COO)
2] the SEM photo of composite Nano band.
Fig. 2 is SnO
2The XRD spectra of/ZnO composite Nano band.
Fig. 3 is SnO
2The SEM photo of/ZnO composite Nano band, this figure double as Figure of abstract.
Fig. 4 is SnO
2The EDS spectrogram of/ZnO composite Nano band.
Fig. 5 is SnO
2The TEM photo of/ZnO composite Nano band.
Fig. 6 is SnO
2/ ZnO composite Nano band the ED photo.
The specific embodiment
Butter of tin (the SnCl that the present invention selected for use
45H
2O) and zinc acetate (Zn (CH
3COO)
22H
2O), polyvinylpyrrolidone (PVP, molecular weight 90000), N, dinethylformamide (DMF) is commercially available analysis net product; Used glass apparatus and equipment are commonly used in the laboratory.
Embodiment 1: take by weighing a certain amount of butter of tin and zinc acetate (mol ratio is 1: 2), be dissolved in an amount of DMF solvent, take by weighing a certain amount of PVP again and join in the above-mentioned solution, stir 6h in the room temperature lower magnetic force, and leave standstill 3h, promptly form spinning solution.The mass percent of this each part of spinning solution is: butter of tin+zinc acetate content 8%, PVP content 19%, DMF content 73%.The spinning solution for preparing is added in the liquid storage pipe of device for spinning, carry out electrostatic spinning, nozzle diameter 0.8mm, the angle of adjustment nozzle and horizontal plane is 15 °, DC voltage is 15kV; The syringe needle nozzle is 13cm to the curing distance of receiving screen; 20 ℃ of indoor temperatures, relative humidity is 45%, obtains PVP/ [SnCl
4+ Zn (CH
3COO)
2] the composite Nano band.With prepared PVP/ [SnCl
4+ Zn (CH
3COO)
2] the composite Nano band is put in the temperature programmed control stove and heat-treats, heating rate is 1 ℃/min, at 600 ℃ of constant temperature 8h, rate of temperature fall is controlled to be 1 ℃/min, reduces to room temperature when cooling to 200 ℃ naturally, promptly obtains SnO
2The compound polycrystal nanobelt of/ZnO.Prepared PVP/ [SnCl
4+ Zn (CH
3COO)
2] composite Nano belt surface smoother is smooth, sees shown in Figure 1.Prepared SnO
2The compound polycrystal nanobelt of/ZnO has good crystal formation, and wherein listed d value and the relative intensity of the diffraction maximum of ZnO and ZnO standard card JCPDS (36-1451) is consistent, and crystal formation is a hexagonal wurtzite, and space group is P6
3Mc; SnO
2Diffraction maximum and the listed d value of standard card JCPDS (41-1445) and relative intensity consistent, be tetragonal crystal system, space group is P4
2/ mnm sees shown in Figure 2.Prepared SnO
2/ ZnO is compound, and polycrystal nanobelt is made up of nano particle, and the width of nano belt is 2～6 μ m, and thickness is 240～600nm, and length is seen shown in Figure 3 greater than 100 μ m.SnO
2The compound polycrystal nanobelt of/ZnO is formed (Au shows plating when coming from the SEM sample preparation Au conductive layer) by Sn, Zn and O element, sees shown in Figure 4.SnO
2/ ZnO is compound, and polycrystal nanobelt is made up of nano particle, and diameter is about 10nm, and is as shown in Figure 5.SnO
2The electron diffraction diagram of the compound polycrystal nanobelt of/ZnO is as shown in Figure 6, visible SnO
2/ ZnO composite Nano band belongs to polycrystalline structure.
Embodiment 2: take by weighing a certain amount of butter of tin and zinc acetate (mol ratio is 1: 2), be dissolved in an amount of DMF solvent, take by weighing a certain amount of PVP again and join in the above-mentioned solution, stir 3h in the room temperature lower magnetic force, and leave standstill 2h, promptly form spinning solution.The mass percent of this each part of spinning solution is: butter of tin+zinc acetate content 10%, PVP content 22%, DMF content 68%.The spinning solution for preparing is added in the liquid storage pipe of device for spinning, carry out electrostatic spinning, nozzle diameter 0.8mm, the angle of adjustment nozzle and horizontal plane is 15 °, DC voltage is 20kV; The syringe needle nozzle is 15cm to the curing distance of receiving screen; 25 ℃ of indoor temperatures, relative humidity is 60%, obtains PVP/ [SnCl
4+ Zn (CH
3COO)
2] the composite Nano band.With prepared PVP/ [SnCl
4+ Zn (CH
3COO)
2] the composite Nano band is put in the temperature programmed control stove and heat-treats, heating rate is 2 ℃/min, at 800 ℃ of constant temperature 10h, rate of temperature fall is controlled to be 1 ℃/min, reduces to room temperature when cooling to 200 ℃ naturally, promptly obtains SnO
2The compound polycrystal nanobelt of/ZnO.Prepared SnO
2The compound polycrystal nanobelt of/ZnO has good crystal formation, and wherein listed d value and the relative intensity of the diffraction maximum of ZnO and ZnO standard card JCPDS (36-1451) is consistent, and crystal formation is a hexagonal wurtzite, and space group is P6
3Mc; SnO
2Diffraction maximum and the listed d value of standard card JCPDS (41-1445) and relative intensity consistent, be tetragonal crystal system, space group is P4
2/ mnm.Prepared SnO
2/ ZnO is compound, and polycrystal nanobelt is made up of nano particle, and the width of nano belt is 2～5 μ m, and thickness is 240～500nm, and length is greater than 100 μ m.
Certainly; The present invention also can have other various embodiments; Under the situation that does not deviate from spirit of the present invention and essence thereof; Those of ordinary skill in the art work as can make various corresponding changes and distortion according to the present invention, but these corresponding changes and distortion all should belong to the protection domain of the appended claim of the present invention.
Claims (1)
1. method for preparing the compound polycrystal nanobelt of tin ash/zinc oxide; It is characterized in that, adopt electrostatic spinning technique, use polyvinylpyrrolidone (PVP) to be high polymer templates; Adopt N; Dinethylformamide (DMF) is a solvent, and the preparation product is the compound polycrystal nanobelt of tin ash/zinc oxide, the steps include:
(1) preparing spinning solution
What used in Xi Yuan and zinc source in the spinning solution is butter of tin and zinc acetate, and high polymer templates employing molecular weight is 90000 PVP, and solvent adopts DMF; Take by weighing mol ratio and be 1: 2 butter of tin and zinc acetate, be dissolved in an amount of DMF solvent, obtain the DMF solution of butter of tin and zinc acetate; Taking by weighing a certain amount of PVP again joins in the DMF solution of described butter of tin and zinc acetate; Stir 3～6h in the room temperature lower magnetic force, and leave standstill 2～3h, promptly form spinning solution; The mass percent of this each part of spinning solution is: butter of tin+zinc acetate content 8～10%, PVP content 19～22%, DMF content 68～73%;
(2) preparation PVP/ [SnCl
4+ Zn (CH
3COO)
2] the composite Nano band
Adopt electrostatic spinning technique, technical parameter is: DC voltage is 15～20kV; The syringe needle nozzle diameter is 0.8mm; The angle of nozzle and horizontal plane is 15 ℃; Nozzle is 13～15cm to the curing distance of receiving screen; 20～25 ℃ of indoor temperatures, relative humidity are 45%～60%;
(3) preparation SnO
2The compound polycrystal nanobelt of/ZnO
With the PVP/ [SnCl that is obtained
4+ Zn (CH
3COO)
2] the composite Nano band carries out heat treatment, technical parameter is: heating rate is 1～2 ℃/min, in 600～800 ℃ of temperature ranges, is incubated 8～10h, rate of temperature fall is controlled to be 1 ℃/min, reduces to room temperature when cooling to 200 ℃ naturally, so far obtains SnO
2The compound polycrystal nanobelt of/ZnO.
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| CN102085380B (en) * | 2010-12-30 | 2012-09-05 | 成都西南交大科技园管理有限责任公司 | Preparation method of nano magnetic particles for detection and treatment of coronary heart diseases |
| CN102214505B (en) * | 2011-03-11 | 2012-09-05 | 长春理工大学 | Preparation method of Nio@Al2O3@TiO2 coaxial three-layer nano cable |
| CN102214506B (en) * | 2011-03-11 | 2012-10-03 | 长春理工大学 | Method for preparing silicon oxide@zinc silicate@silicon oxide three-layer coaxial nano cable |
| CN102222548B (en) * | 2011-03-11 | 2012-10-03 | 长春理工大学 | Method for preparing NiO@SnO2@Zn2TiO4@TiO2 coaxial four-layer nanocable |
| CN103105419B (en) * | 2011-11-09 | 2015-06-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of alumina-tin oxide composite nanotube |
| CN103011257B (en) * | 2013-01-05 | 2014-06-11 | 青岛大学 | Preparation method of P-type zinc oxide micro/nano fibers |
| CN105013470A (en) * | 2015-07-01 | 2015-11-04 | 宁波工程学院 | Application of ZnO mesoporous nanofiber in photocatalysts |
| CN107142556B (en) * | 2017-06-01 | 2019-06-11 | 济南大学 | A kind of SnO2The preparation method and products thereof of/ZnO composite micro-nano rice fiber |
| CN111349974A (en) * | 2020-03-12 | 2020-06-30 | 重庆大学 | Preparation method of nanofiber hydrogen sensing material subjected to plasma treatment |
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| CN101239737A (en) * | 2008-02-29 | 2008-08-13 | 中国科学院理化技术研究所 | Titanium dioxide thin film material with hierarchical structure and preparation method thereof |
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